WO2007029667A1

WO2007029667A1 - Hydrogenation catalyst for carbonyl group, method for producing same, and method for producing unsaturated alcohol by using such catalyst

Info

Publication number: WO2007029667A1
Application number: PCT/JP2006/317493
Authority: WO
Inventors: Yasunobu Inoue; Hiroshi Nishiyama; Nobuo Saito; Junichi Takeuchi
Original assignee: National University Corporation Nagaoka University Of Technology
Priority date: 2005-09-07
Filing date: 2006-09-05
Publication date: 2007-03-15
Also published as: JP4862162B2; US20090299105A1; EP1930075A1; JPWO2007029667A1

Abstract

Disclosed is a hydrogenation catalyst for carbonyl groups which enables to produce an unsaturated alcohol by economically hydrogenating an unsaturated carbonyl compound with high selectivity by a simple process. Also disclosed are a method for efficiently producing such a hydrogenation catalyst, and a practical method for producing an unsaturated alcohol by using such a hydrogenation catalyst. Specifically disclosed is a hydrogenation catalyst obtained by loading a noble metal such as ruthenium as a catalyst component onto a carrier which is composed of a gallium compound containing oxygen. Gallium oxyhydroxide, gallium oxide, gallium phosphate or the like can be used as the gallium compound, and a hydrogenation catalyst wherein 0.1-10% by weight of ruthenium is loaded on such a gallium compound carrier is used suitably.

Description

Specification

Catalyst for hydrogenation of carbonyl group, method for producing the same, and method for producing unsaturated alcohols using the catalyst

Technical field

[0001] The present invention uses a hydrogenation catalyst for a carbonyl group in which a noble metal such as ruthenium (Ru) or platinum (Pt) is supported on a gallium compound carrier, a production method thereof, and the hydrogenation catalyst. The present invention relates to a process for producing an unsaturated alcohol by selectively hydrogenating an unsaturated carbonyl compound.

Background art

[0002] Unsaturated alcohols such as nerol and gera-ol are important compounds as intermediates for producing organic compounds useful as synthetic resins, pharmaceuticals, perfumes and the like. This unsaturated alcohol is produced by hydrating the corresponding unsaturated carboxylic compound in the presence of a hydrogenation catalyst.

[0003] Conventionally, various hydrogenation catalysts used for the production of unsaturated alcohols are known, and examples thereof include a ruthenium Z iron catalyst supported on carbon (Patent Document 1).

2). In addition, a catalyst comprising a ruthenium derivative associated with a water-soluble ligand or a complex salt of ruthenium and a water-soluble ligand has also been proposed (see Patent Documents 3 and 4).

Patent Document 1: JP-A-58-27642

Patent Document 2: Japanese Patent Laid-Open No. 2003-24555

Patent Document 3: Japanese Patent No. 2520461

Patent Document 4: Japanese Patent No. 2549158

[0004] However, the prior arts of Patent Documents 1 and 2 require the use of three components of a carbon support, ruthenium, and iron, and the production of the catalyst becomes complicated. Furthermore, to improve the selective hydrogenation rate to unsaturated alcohol, methanol and trimethylamine are added to the catalytic reaction system to separate these components from the reaction product. A processing step is required. In the prior arts of Patent Documents 3 and 4, the hydrogenation reaction is performed in a medium containing an organic solvent, which increases the cost. Also, there is When a distillation step is required to remove the solvent, there is a problem.

[0005] Further, the catalyst support includes at least one metal selected from group VIII power and at least one selected from the group consisting of germanium, tin, lead, rhenium, gallium, indium, gold, silver, and thallium. A catalyst supporting an additional element M is also known (see Patent Document 5). However, this hydrogenation catalyst requires the use of three components including the catalyst carrier, and the production of the catalyst becomes complicated. Moreover, in this catalyst, gallium used as the additional element M is considered to exist in a metallic state because of its production method capability. In order to increase the selectivity of the unsaturated alcohol when performing selective hydrogenation of the unsaturated carboxylic compound to the unsaturated alcohol using this catalyst, a solvent such as n-heptane is used. It is necessary to dilute the unsaturated carboxylic compound as a raw material, and a distillation step is required to remove the organic solvent.

Patent Document 5: USP6, 294, 696

Disclosure of the invention

Problems to be solved by the invention

[0006] Therefore, the present invention can solve the above-mentioned problems of the prior art, and can produce an unsaturated alcohol by hydrogenating an unsaturated carbonyl compound with high selectivity and economically by a simple process. An object of the present invention is to provide a hydrogenation catalyst for a carbonyl group and an efficient production method thereof. Another object of the present invention is to provide a practical method for producing unsaturated alcohol using the hydrogenation catalyst.

Means for solving the problem

As a result of intensive studies, the present inventors have found that the above problem can be solved by forming a hydrogenation catalyst by supporting a noble metal such as ruthenium or Pt as a catalyst component on a carrier made of a gallium compound. Discovered and completed the present invention.

That is, in the present invention, the following configurations 1 to 13 are adopted.

1. A hydrogenation catalyst for a carbonyl group in which a noble metal is supported on a gallium compound carrier containing oxygen.

2. The hydrogenation catalyst according to 1, wherein the gallium compound containing oxygen is selected from gallium oxyhydroxide, gallium oxide, and gallium phosphate. 3. The hydrogenation catalyst according to 1 or 2, wherein 0.1 to 10% by weight of ruthenium is supported on a gallium compound carrier containing oxygen.

4. Further 0.1-: The hydrogenation catalyst according to 3, wherein platinum of LO weight% is supported.

5. 1) A step of suspending a gallium compound carrier containing oxygen in water,

2) adding a solution of a noble metal salt that is a catalytically active component to the suspension;

3) A step of adding a water-soluble reducing agent to reduce the catalytically active component and depositing the catalytically active component on the carrier,

A method for producing a hydrogenation catalyst for a carbonyl group in which a noble metal is supported on an oxygen-containing gallium compound carrier.

6. In addition,

4) a step of separating the catalyst having the catalytically active component deposited on the carrier from the aqueous phase of the carrier suspension, and 5) a step of drying the separated catalyst,

6. The method for producing a hydrogenation catalyst according to 5, wherein

7. Select the water-soluble reducing agent in step 3) as methanol, ethanol, formaldehyde, sodium phosphinate, dimethylamine borane, sodium borohydride, potassium borohydride, lithium borohydride, lithium aluminum hydride or hydrazine. The method for producing a hydrogenation catalyst according to 5 or 6, wherein

8. The catalytically active component in step 2) is a ruthenium salt, nitrate, nitrosyl nitrate, acid salt, hydroxide, acetylylacetonate complex, pyripyridine complex or ammine complex. A method for producing a hydrogenation catalyst according to any one of 5 to 7.

9. After depositing ruthenium as a catalytically active component on the support in step 3), 3-1) suspending the separated catalyst again in water, 3-2) platinum salt in the suspension. 9. The hydrogenation catalyst according to 8, characterized by comprising: a step of caloricizing the solution; and 3-3) a step of adding a water-soluble reducing agent to reduce the platinum salt and further depositing platinum on the catalyst. Production method. 10. An unsaturated carbon compound represented by the following formula (1) is hydrogenated in the presence of the hydrogenation catalyst described in any one of 1 to 4, Method for producing unsaturated alcohol represented by (2): [Chemical 1]

C H 1 O H

[Wherein, each of R and R is the same or different and is a hydrogen atom, C1-C10

1 2

Represents a saturated or unsaturated aliphatic group, a saturated or unsaturated alicyclic group, or an aromatic group, and at least one of R and R is a force containing an ethylene double bond or R

1 2 1 and R together form an ethylenically unsaturated alicyclic group, said aliphatic group, alicyclic

2

Each group or aromatic group is substituted with one or more identical or different groups of a C1-C4 alkyl group, a hydroxyl group or a C1-C4 alkoxy group!

11. The method for producing an unsaturated alcohol according to 10, wherein the carbonyl compound represented by the formula (1) is a, j8-unsaturated carbonyl compound.

12. The process for producing an unsaturated alcohol according to 10 or 11, characterized in that it is citral, a carboxylic compound compound represented by formula (1).

13. The method for producing an unsaturated alcohol according to any one of 10 to 12, wherein the unsaturated carbonyl compound is hydrogenated without diluting with a solvent.

The invention's effect

The use of a gallium compound containing oxygen as a carrier as a hydrogenation catalyst for a carbonyl group is novel, and the present invention has the following remarkable effects.

1) The hydrogenation catalyst of the present invention is basically a two-component force consisting of a carrier composed of a gallium compound containing oxygen and ruthenium, and can be manufactured easily and at low cost.

2) By using the novel catalyst of the present invention, an unsaturated alcohol can be produced by hydrogenating an unsaturated carbonyl compound with high selectivity.

3) Unsaturated alcohols can be produced without using solvents or auxiliaries. The alcohol production process becomes simple and the cost can be significantly reduced.

Brief Description of Drawings

FIG. 1 is an electron micrograph of an oxygallium oxyhydroxide carrier obtained in Example 1.

FIG. 2 is an electron micrograph of the gallium oxide carrier obtained in Example 2.

FIG. 3 is an electron micrograph of the gallium phosphate carrier obtained in Example 3.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] In the present invention, a noble metal such as ruthenium is supported as a catalyst component on a gallium compound carrier containing oxygen to constitute a hydrogenation catalyst for a carbonyl group. The supported amount of the catalyst component with respect to the gallium compound is preferably 0.1 to 10% by weight, particularly 1 to 3% by weight.

[0011] The oxygen-containing gallium compound used as a carrier is not particularly limited, but preferred gallium compounds include oxygallium oxygallium, gallium oxide, gallium phosphate, and the like. These gallium compounds may be prepared by a conventional method when producing a hydrogenation catalyst, but commercially available products can also be used. In addition, the surface of another carrier such as porous silica coated with a gallium compound can be used as the carrier. There are no particular restrictions on the shape and size of the carrier, but usually fine particles of about 1 to 30 / ζ πι, flakes, or porous materials are used.

When ruthenium or the like is supported using metallic gallium as a carrier, the melting point of metallic gallium is 29.8 ° C, so that gallium dissolves under the hydrogenation conditions of the carbo-louis compound, and aggregation occurs. It occurs violently and does not function as a catalyst. In the present invention, such a problem is solved by using a gallium compound containing oxygen as a carrier.

[0012] Hereinafter, the case of using ruthenium as a catalytically active component will be described as an example and the hydrogenation catalyst for a carbonyl group of the present invention will be described.

The hydrogenation catalyst of the present invention can be produced, for example, by the following procedure.

1) a step of suspending a gallium compound carrier containing oxygen in water;

2) adding a metal salt solution of ruthenium, which is a catalytically active component, to the suspension; 3) A step of adding a water-soluble reducing agent to reduce the catalytically active component and depositing the catalytically active component on the carrier.

Instead of the above step 3), 3 ′) the carrier suspension added with the catalytically active component is evaporated to dryness, calcined in air at 200 to 500 ° C. and then in a hydrogen stream at 200 to 600 ° C. It is possible to adopt a reduction process.

[0013] Also, usually after the above steps,

4) separating the catalyst having the catalytically active component deposited on the carrier from the aqueous phase of the carrier suspension; and

5) drying the separated catalyst,

Is adopted.

[0014] As the catalytically active component in the above step 2), ruthenium salts, nitrates, nitrosyl nitrates, oxides, hydroxides, acetylylacetonate complexes, piperidine complexes, ammine complexes, etc. Used. These catalyst components are usually added to the carrier suspension as an aqueous solution. In addition to the catalytically active components, alkali metal salts such as lithium, sodium, potassium, rubidium and cesium salts, nitrates and carbonates may be included.

[0015] Examples of the water-soluble reducing agent in the above step 3) include methanol, ethanol, formaldehyde, sodium phosphinate, dimethylamine borane, sodium borohydride, potassium borohydride, lithium borohydride, lithium hydride. Examples thereof include aluminum and hydrazine. These can be used alone or in combination of two or more.

[0016] Further, after depositing ruthenium as a catalytically active component on the support in step 3), 3-1) a step of suspending the separated catalyst again in water; 3-2) platinum in the suspension A step of adding a salt solution; and 3-3) a step of adding a water-soluble reducing agent to reduce the platinum salt and further depositing gold on the catalyst, and hydrogen carrying ruthenium and platinum as catalyst components. A catalyst for conversion may be produced. Such a catalyst can exhibit even higher catalytic activity.

Next, an example of producing the hydrogenation catalyst of the present invention using gallium oxide, oxygallium oxyhydroxide, and gallium phosphate as a carrier will be described in more detail. It is not intended to limit the invention. [0018] (Production of ruthenium Z gallium oxide catalyst)

Dissolve gallium nitrate in ethanol, stir and drop the aqueous ammonia solution to raise the pH, keep the pH in the range of 5-6, and continue stirring for 1-3 hours, gel precipitation of gallium hydroxide Get. The obtained precipitate of gallium hydroxide is suction filtered and calcined in the atmosphere at a temperature of 500 ° C. to 800 ° C. to obtain an oxygallium carrier.

Further, commercially available gallium oxalate can also be used as a carrier.

[0019] Suspend the obtained gallium oxide carrier in distilled water [Step 1)], add the active ingredient ruthenium in the form of a metal salt solution, and stir for 30 minutes to 1 hour [Step 2) ]. Next, the temperature of the suspension is set to room temperature to 70 ° C., and a water-soluble reducing agent is slowly added to simultaneously support and reduce the active ingredient, ruthenium [Step 3)].

Next, this suspension solution is filtered with suction to separate the ruthenium Z gallium oxide catalyst from the aqueous phase [Step 4], washed with isopropyl alcohol or ethanol, and dried at room temperature in the atmosphere [ Step 5)].

In step 2) above, the alkali metal salt and the lanthanoid metal salt can be added simultaneously or each.

Alternatively, as an alternative to the above-described method using liquid phase reduction, the carrier suspension to which the catalytically active component is added is evaporated to dryness, and the component is calcined in air at a temperature of 200 ° C to 500 ° C. You can also use a method of reducing at 200 ° C to 600 ° C in a hydrogen stream!

[0020] (Production of ruthenium Z gallium phosphate catalyst)

Dissolve gallium nitrate in distilled water, add phosphoric acid to this solution, stir, add dropwise aqueous ammonia solution to raise the pH, and stir in the pH range of 4-6 for 1-3 hours to obtain a white precipitate. The precipitate is filtered with suction, dried at a temperature of 100 to 200 ° C, and calcined at a temperature of 800 ° C to 1200 ° C in the air to obtain a gallium phosphate carrier.

[0021] The obtained gallium carrier is suspended in distilled water [Step 1), and ruthenium, which is an active ingredient, is added in the form of a metal salt solution and stirred for 30 minutes to 1 hour [Step 2)]. Next, the temperature of the suspension is set to room temperature to 70 ° C., and a water-soluble reducing agent is slowly added to simultaneously support and reduce ruthenium, which is an active ingredient [Step 3)].

The suspension is then filtered with suction to remove the ruthenium Z gallium phosphate catalyst from the aqueous phase. Separate [Step 4), wash with isopropyl alcohol or ethanol, and dry at room temperature in the atmosphere [Step 5)].

[0022] In the above step 2), the alkali metal salt and the lanthanoid metal salt can be added simultaneously or respectively.

[0023] (Manufacture of ruthenium Z-oxyhydroxide catalyst)

Add ammonia power, urea, or hexamethylenetetramine to the gallium nitrate aqueous solution, and stir overnight at a liquid temperature of 20 ° C to 50 ° C. Furthermore, a white precipitate is obtained by stirring at a liquid temperature of 70 ° C to 90 ° C for 2 hours. The precipitate is cooled and filtered, washed with isopropyl alcohol or ethanol, and dried at room temperature to 350 ° C. to obtain a gallium oxyhydroxide carrier.

In addition, gallium nitrate is pulverized in a mortar and baked in the air at a temperature range of 200 to 400 ° C for 5 to 20 hours to obtain δ gallium gallate, and this δ gallium monoxide is mixed with distilled water. Then, hydrothermal synthesis is carried out in an autoclave at a temperature range of 150 to 300 ° C. for 24 to 48 hours to obtain an gallium oxyhydroxide carrier.

Furthermore, commercially available oxygallium oxyhydroxide can also be used as a carrier.

[0024] The obtained oxygallium oxyhydroxide carrier is suspended in distilled water [Step 1], ruthenium as an active ingredient is added in the form of a metal salt solution, and the mixture is stirred for 30 minutes to 1 hour [Step 2]. )]. Next, the temperature of the suspension is set to room temperature to 70 ° C., and a water-soluble reducing agent is slowly added to simultaneously carry and reduce ruthenium as an active ingredient [step 3)].

Next, this suspension solution is filtered with suction, and the ruthenium Zoxy gallium hydroxide catalyst is separated by water phase [Step 4], and washed with isopropyl alcohol or ethanol at room temperature in the atmosphere. Perform drying [Step 5).

[0025] In the above step 2), the alkali metal salt and the lanthanoid metal salt can be added simultaneously or respectively.

In addition, as an alternative to the above-described method using liquid phase reduction, a carrier added with a catalytically active component The suspension may be evaporated to dryness, and the components may be calcined in air at a temperature of 200 ° C to 500 ° C and then reduced to 200 ° C to 600 ° C in a hydrogen stream! ,.

The hydrogenation catalyst of the present invention is basically a two-component power of a carrier composed of a gallium compound containing oxygen and ruthenium, and can be manufactured easily and at low cost.

[0026] By using the hydrogenation catalyst for the carbonyl group of the present invention, the unsaturated carbonyl compound represented by the following formula (1) is selectively hydrogenated and represented by the formula (2). Can be produced efficiently.

[0027] [Chemical 2]

Ri Ri

, C = O> C H

^R2 , R ₂ ^

(1) (2)

[Wherein, each of R and R is the same or different and is a C1-C10 hydrogen atom.

1 2

, A saturated or unsaturated aliphatic group, a saturated or unsaturated alicyclic group, or an aromatic group, and at least one of R and R is a force containing an ethylenic double bond, or R

1 2 1 and R together form an ethylenically unsaturated alicyclic group.

2

Each of the cyclic group or aromatic group may be substituted with one or two or more identical or different groups of a C1-C4 alkyl group, a hydroxyl group, or a C1-C4 alkoxy group.

[0029] Specific examples of R and R include, for example, hydrogen; methyl, ethyl, propyl, isopropyl

1 2

, N-butyl, i-butyl, t-butyl, pentyl, hexyl, heptenyl, octyl ゝ noninore, decinole , 1-methynole-2-pentenyl, isopropenyl, 1-butenyl, hexenyl, otatur, nonel or decyl; benzyl, phenol or naphthyl; Each of these may be substituted with one or two or more identical or different groups of a C1-C4 alkyl group, a hydroxyl group, or a C1-C4 alkoxy group. [0030] Preferred unsaturated carbo-louie compound represented by the formula (1) includes, for example, citronellal, H-geralacetone, H-nerolidol, methyl vinyl ketone, mesityl oxide, pseudoionone, Examples include dihydrofalcenelacetone, rismeral, methylhexenone and the like. Particularly preferred unsaturated carbo-louis compounds include citronellal or 0; β-unsaturated carbole compounds such as acrolein, methacrolein, crotonaldehyde, prenal, farnesal or citral. Of these, citral is more preferred.

[0031] Citral includes citral Α (trans isomer) represented by the following formula (3) and citral B (cis isomer) represented by formula (4). When hydrogenated, the target gera-ol represented by formula (5) and nerol represented by formula (6), as well as citronellal represented by formula (7), citronellol represented by formula (8), Furthermore, tetrahydrogeraol of the formula (9) is produced.

[0032] [Chemical 3]

(7) (8)

When the hydrogenation catalyst of the present invention is used, an aldehyde can be obtained with high selectivity without using a solvent for diluting the raw materials required for conventional hydrogenation catalysts and additives such as trimethylamine. Only groups can be hydrogenated. In addition, by-product formation can be suppressed, and geraniol and nerol can be obtained with high yield. Therefore, it is possible to easily separate and purify the target product, greatly increasing the production cost of the product. It can be reduced.

Example

Hereinafter, the present invention will be further described with reference to examples. However, these specific examples do not limit the present invention.

(Example 1: Production of ruthenium Zoxyhydroxy-gallium catalyst)

500 mL of distilled water was added to a 1 L separable flask, and 13.64 g of gallium nitrate was dissolved. To this solution, 70.13 g of hexamethylenetetramine was added and stirred at room temperature for 12 hours and then at 90 ° C. for 2 hours. After cooling the solution, the resulting precipitate was suction filtered, washed with isopropyl alcohol, and then dried at 300 ° C. in the air to obtain a gallium oxyhydroxide carrier. An electron micrograph of the obtained gallium oxyhydroxide carrier is shown in FIG. This gallium oxyhydroxide 2. Og was suspended in 200 mL of distilled water, and 0.11414 g of ruthenium chloride was added and stirred. A solution obtained by dissolving 2 g of sodium borohydride in 50 mL of distilled water was slowly added dropwise, followed by liquid phase reduction with stirring for 2 hours, to support 2.5 wt% of ruthenium.

Next, the catalyst suspension carrying ruthenium was suction filtered, washed with distilled water and ethanol, and dried in the atmosphere at room temperature to obtain a ruthenium Zoxy gallium hydroxide catalyst.

Example 2 Production of Ruthenium Z Gallium Oxide Catalyst

In a 500 mL beaker, 200 mL of ethanol was placed and 13.7 g of gallium nitrate was dissolved. An aqueous ammonia solution was added dropwise to the solution to raise the pH of the solution to 5.2. The mixture was stirred at room temperature for 2 hours to obtain a gel-like gallium hydroxide precipitate. The resulting precipitate was filtered by suction and fired at 800 ° C. in the air to obtain a gallium oxide carrier. An electron micrograph of the obtained gallium oxide carrier is shown in FIG.

1.5 g of this gallium oxide was suspended in 30 mL of ethanol, 0.148 g of ruthenium acetylethyl acetate complex was added, and the mixture was stirred at 60 ° C. for 3 hours. The suspension was evaporated to dryness, heated in air at 150 ° C, and then reduced in a hydrogen stream at 400 ° C to obtain a ruthenium Z-gallium oxide catalyst carrying 2.5 wt% ruthenium. Obtained.

(Example 3: Production of ruthenium Z gallium phosphate catalyst) Distilled water (200 mL) was added to a 500 mL beaker to dissolve 15.5 g of gallium nitrate. To this solution, 4.8 g of phosphoric acid was stirred. An aqueous ammonia solution was added dropwise to this solution to raise the pH of the solution to 5.0. Stirring was performed for 1 hour to obtain a white precipitate. The precipitate was filtered by suction, heated in the atmosphere at 160 ° C for 2 hours, and calcined in the atmosphere at 1000 ° C to obtain a gallium phosphate carrier. An electron micrograph of the obtained gallium phosphate carrier is shown in FIG.

1.5 g of this gallium phosphate was suspended in 30 mL of ethanol, 0.086 g of ruthenium chloride and 0.026 g of rubidium nitrate were added, and the mixture was stirred at 60 ° C. for 3 hours. The suspension is evaporated to dryness, heated in air at 150 ° C for 1 hour, and then reduced at 400 ° C in a steam flow to 2.5 weight ⁰ /. Ruthenium-supported ruthenium Z gallium phosphate catalyst

[0037] (Example 4: Selective hydrogenation of citral)

2 g of the catalyst powder obtained in Example 1 was introduced into an autoclave having a volume of 200 mL, and 130 mL of citral was added thereto. After sealing the autoclave, nitrogen gas was introduced and evacuated three times at IMPa pressure while stirring, and then the nitrogen gas was replaced with 1.3 MPa hydrogen gas and heated to 120 ° C. During hydrogenation, samples were taken from the reaction vessel at regular time intervals and analyzed by gas chromatography.

Table 1 shows the conversion rate of citral, the selection rate of nerol Z geraniol produced at the conversion rate, and by-products.

[0038] [Table 1] Selectivity of citral products (%)

Conversion rate (%) Ne-Zuil Z Sito [Non-Ra Citronellol Tetrahydro Unknown substance

Geraniol Geranio

1 1. 3 5 1 0 0 0 0 0 0 0 0. 0 0 0. 0 0 0. 0 0

3 5. 4 4 9 7. 5 2 0 0 0 0. 0 0 0. 0 0 2-4 8

5 5. 3 2 9 6. 8 0 0 0 0 0. 8 6 0. 0 0 2. 3 4

6 0. 8 7 9 6. 9 0 0 0 0 0. 8 7 0. 0 0 2. 2 3

8 4. 7 2 9 6. 4 4 0 0 0 1. 4 0 0. 0 0 2. 1 6

(Example 5)

1.5 g of the catalyst powder obtained in Example 2 was introduced into an autoclave having a volume of lOOmL, and 65 mL of citral was added thereto. After sealing the autoclave, After introducing and evacuating nitrogen gas three times at a pressure of 1, the nitrogen gas was replaced with 1.3 MPa hydrogen gas and heated to 120 ° C. During hydrogenation, samples were taken from the reaction vessel at regular time intervals and analyzed by gas chromatography.

Table 2 shows the conversion rate of citral, the selection rate of nerol Z geraniol produced at the conversion rate, and by-products.

[¾2]

[Example 6]

1.5 g of the catalyst powder obtained in Example 3 was introduced into an autoclave having a volume of lOOmL, and 65 mL of citral was added thereto. After sealing the autoclave, nitrogen gas was introduced and evacuated three times at IMPa pressure while stirring, and then the nitrogen gas was replaced with 1.3 MPa hydrogen gas and heated to 120 ° C. During hydrogenation, samples were taken from the reaction vessel at regular time intervals and analyzed by gas chromatography.

Table 3 shows the conversion rate of citral, the selection rate of nerol Z-geraol produced at the conversion rate, and by-products.

[0042] [Table 3]

[0043] (Example 7) The gallium oxyhydrate 2. Og produced in the procedure of Example 1 was suspended in 200 mL of distilled water, and 0.134 g of ruthenium chloride was added and stirred. A solution obtained by dissolving 2 g of sodium borohydride in 50 mL of distilled water was slowly dropped, and stirring was continued for 2 hours to perform liquid phase reduction to support 2.5% by weight of ruthenium. The catalyst suspension solution carrying ruthenium was filtered off with suction, and the catalyst was washed with distilled water and ethanol. This catalyst was again suspended in 200 mL of distilled water, and 0.133 g of salt 匕 platinum (IV) acid hexahydrate was dissolved in this suspension solution. Then, a solution of sodium borohydride 2g of distilled water 50mL and Yutsu chestnut dropwise performs continued liquid phase reduction stirred for 2 hours, Okishi water acid I carrying ruthenium 2.5 weight ^_0/0 An additional 2.5% by weight of platinum was supported on the gallium catalyst. The catalyst suspension was filtered with suction, washed with distilled water and ethanol, and then dried in the air to obtain a catalyst containing ruthenium and platinum as catalyst components.

[0044] (Example 8)

2 g of the catalyst powder obtained in Example 7 was introduced into an autoclave having a volume of 200 mL, and 130 mL of citral was added thereto. After sealing the autoclave, nitrogen gas was introduced and evacuated three times at IMPa pressure while stirring, and then the nitrogen gas was replaced with 1.3 MPa hydrogen gas and heated to 120 ° C. During hydrogenation, samples were taken from the reaction vessel at regular time intervals and analyzed by gas chromatography.

Table 4 shows the conversion rate of citral, the selection rate of nerol Z-geraol produced at the conversion rate, and by-products.

[0045] [Table 4] Reaction time Selectivity of citral product (%)

(Time) Conversion rate (%) Neroril Z 卜 Ronella ル L 卜ネ Nellore Unknown substance

Geraniol

1 2 1. 2 9 8. 5 1 N D N D 1.4 9

3 6 2. 6 9 7. 7 0 N D 0. 8 0 1. 9 0

3, 5 8 1.5 5 7 7.2 3 N D 0.8 8 8 1.8 9

4 9 1 .9 9 6 .9 7 N D 1.0 .0 5 1 .9 7

[0046] As described above, as the present invention, carbonyl having ruthenium supported on a gallium compound carrier In the present invention, a noble metal such as Pt, Rh, Ir, or Co can be used as a catalyst active component.

For example, when Pt is used as the catalytically active component, the conversion rate of citral is reduced compared to ruthenium when compared with the same reaction time S, and the selectivity of nerol Z gera-ol is 100%. Therefore, other noble metals can be selected as the catalytic active component depending on the application.

Example 9 Production of PtZoxygallium hydroxide catalyst

Oxygallium oxyhydroxide 2. Og was suspended in 200 mL of distilled water, and 0.133 g of chloroplatinic acid was added and stirred. A solution obtained by dissolving 2 g of sodium borohydride in 50 mL of distilled water was slowly added dropwise, followed by liquid phase reduction by continuing stirring for 2 hours, and loading 2.5 wt% Pt. Next, loading Pt The catalyst suspension was filtered with suction, washed with distilled water and ethanol, and dried in the atmosphere at room temperature to obtain a PtZ oxygallium gallium catalyst.

As the catalytically active component, instead of salt / platinic acid, salt / first platinum ammonia, salt / second platinum ammonia, or the like can be used.

[0048] (Example 10)

2 g of the catalyst powder obtained in Example 9 was introduced into an autoclave having a volume of 200 mL, and 130 mL of citral was added thereto. After sealing the autoclave, nitrogen gas was introduced and evacuated three times at IMPa pressure while stirring, and then the nitrogen gas was replaced with 1.3 MPa hydrogen gas and heated to 120 ° C. During hydrogenation, samples were taken from the reaction vessel at regular time intervals and analyzed by gas chromatography.

At a reaction time of 6 hours, the conversion rate of citral was 9.8%, and the selectivity for nerol Z-geraol was 100%.

Claims

The scope of the claims

[1] A catalyst for hydrogenation of a carbonyl group in which a noble metal is supported on a gallium compound carrier containing oxygen.

[2] The hydrogenation catalyst according to claim 1, wherein the oxygen-containing gallium compound is selected from gallium oxyhydroxide, gallium oxide, and gallium phosphate.

[3] The hydrogenation catalyst according to [1] or [2], wherein 0.1 to: LO wt% ruthenium is supported on a gallium compound carrier containing oxygen.

[4] The hydrogenation catalyst according to claim 3, further comprising 0.1 to: platinum of LO weight%.

[5] 1) A step of suspending a gallium compound carrier containing oxygen in water,

[6] In addition,

The method for producing a hydrogenation catalyst according to claim 5, comprising:

[7] The water-soluble reducing agent in step 3) is methanol, ethanol, formaldehyde, sodium phosphinate, dimethylamine borane, sodium borohydride, potassium borohydride, lithium borohydride, lithium aluminum hydride or hydrazine. The method for producing a hydrogenation catalyst according to claim 5 or 6, wherein the force is also selected.

[8] The catalytically active component of step 2) is characterized in that it is a ruthenium salt, nitrate, nitrosyl nitrate, acid salt, hydroxide, acetylacetonate complex, a pyridine complex or an ammine complex. A method for producing a hydrogenation catalyst according to any one of claims 5 to 7.

[9] After depositing ruthenium as a catalytically active component on the support in step 3), 3-1) suspending the separated catalyst in water again, 3-2) platinum salt in the suspension. Add the solution 9. The process for producing a hydrogenation catalyst according to claim 8, further comprising the steps of: 3) 3) adding a water-soluble reducing agent to reduce the platinum salt, and further depositing platinum on the catalyst. Method. An unsaturated carbonyl compound represented by the following formula (1) is hydrogenated in the presence of the hydrogenation catalyst according to any one of claims 1 to 4. Method for producing unsaturated alcohol represented by (2):

[Chemical 1]

Ri R i

, C = O> C H

R2 z R ₂

(1) (2) [wherein R and R are the same or different and each represents a hydrogen atom, C1 to C10

1 2

2

[11] The method for producing an unsaturated alcohol according to [10], wherein the carboxylic compound represented by the formula (1) is an α, j8-unsaturated carbonyl compound.

12. The method for producing an unsaturated alcohol according to claim 10 or 11, wherein the compound is a carbo-Louis compound strength citral represented by the formula (1).

[13] The method for producing an unsaturated alcohol according to any one of [10] to [12], wherein the unsaturated carbonyl compound is hydrogenated without diluting with a solvent.